Fire-resistant polyurethanes prepared from adducts of hexahalocyclopentadiene dicarboxylic acids and a monomeric 1, 2-epoxide



United States Patent 6 Claims. (Cl. 260-25) This is a division ofapplication Ser. No. 302,439, now US. Patent No. 3,278,580, which wasfiled Aug. 15, 1963, as a continuation-in-part of application Ser. No.25,520, filed Apr. 29, 1960, now abandoned, which is acontinuation-in-part of application Ser. No. 853,689 now US. Patent No.3,055,850.

This invention relates to novel resinous compositions and method forpreparing same. More particularly, the present invention resides inpolyurethane compositions useful for many applications, for example, inthe preparation of flame retardant rigid and flexible polyurethanefoams, flame retardant polyurethane surface coatings, flame retardantpolyurethane elastomers or synthetic rubbers, flame retardant adhesives,and the like. The resinous compositions of the invention are also usefulin the preparation of polyester resins, particularly unsaturatedpolyester resins. Other uses include the preparation of plasticizers.

The methods of the prior art have attained fire-resistance in rigidfoams by the use of various plasticizing substances, such as the variousphosphate or phosphonate esters or chlorinated compounds. However, suchplasticizing substances are additives which are not chemically combinedwith the polyurethane plastic and are progressively lost from theplastic by evaporation, leaching, and the like. Consequently, theproduct does not have a permanently reduced flammability. Furthermore,the plasticizing additive affects the physical properties of theproduct. Alternatively, the art has incorporated chlorine containingcompounds into the resultant product, for example, Ser. No. 623,795,Fire Resistant Foams, filed Nov. 23, 195 6, now abandoned, but refiledas Ser. No. 311,225, new U.S. Patent 3,156,659, which incorporates anadduct of hexac-hlorocyclopentadiene. Although this method overcomes thedisadvantages inherent in the use of plasticizing substances, it hasbeen found that the incorporation of the chlorine containing compoundinto the polyester causes a rapid increase in viscosity, and solidcompositions usually result at a chlorine content greater than fifteenpercent, therefore requiring special handling or other procedures toobtain a polyurethane foam :of high chlorine content.

Most flexible polyurethane foams are claimed to be fire resistant per seand, therefore, very little has been done to increase the fireresistance of those materials. The claimed fire resistance, however,usually is based on the fact that such materials are self-extinguishingwhen the foams are ignited by virtue of the fact that the burningelastomeric material melts and falls away from the-article thusextinguishing the flame. The melt, however, is flammable and will burnif ignited.

It is, therefore, an object of the present invention to provide resinouscompositions which overcome the aforementioned disadvantages of theprior art. It is a further object of the present invention to provideresinous compositions having a high halogen content which are useful formany purposes, including the preparation of flameretardant polyurethanefoams, adhesives, coating composi- 3,391,092 Patented July 2, 1968 "icetions and elastomers, which compositions are liquid at room temperatureand thereby can be handled by conventional metering and pumpingequipment. It is a further object of the present invention to provideresinous compositions which can be easily and inexpensively prepared,and which can be used to easily and inexpensively prepare productshaving excellent physical characteristics. It is a still further objectof the present invention to provide foamable compositions which can beeasily and rapidly varied so as to provide permanently fire resistantpolyurethane foams with a wide range of physical properties, rangingfrom rigid foams to semi-rigid foams to those flexible foams suitablefor cushioning materials and the like. An additional object of thepresent invention is to prepare truly fire resistant polymers andpolymeric materials, and also truly fireresis-t-ant polyurethane foamsin both the solid and molten state. Further objects and advantages ofthe present invention will appear hereinafter.

In accordance with the present invention, it has been found that highhalogen-containing, resinous compositions which are liquid at roomtemperature and which accomplish the foregoing objectives of the presentinvention can be prepared by reacting together (A) one mole of adicarboxylic acid adduct of -hexahalocyclopentadiene and a dicarboxyliccompound containing aliphatic carbon to carbon uns-aturation, and (B) atleast four moles of a monomeric 1,2-epoxide.

The resulting compositions have the folowing formula:

wherein X is a halogen selected from the group consisting of fluorine,chlorine, bromine, and mixtures thereof, R is a residue of a monomeric1,-2-epoxide, R and R are hydrogen or alkyl radicals having 1 to 4carbon atoms, R and R are hydrocarbon radicals having 1 to '6 carbonatoms, y is an integer from 0 to 1, and m and n are integers from 1 to10, wherein m+n is at least 4. Usually m and n are at least 2. Wherelower viscosity products are desired, the values of m and n should be atleast 3, and more preferably at least 4. Where higher halogen-contentproducts are desired, the values of m and It should not exceed about 6.R and \R are preferably hydrogen or methyl, but can be ethyl, propyl orbutyl or combinations thereof. R and R, can be straight chain orbranched chain alkyl such as methyl, ethyl, propyl, isopropyl, and thelike; alkenyl 'wherein the unsaturation occurs in either the main chainor a branched chain; as well as combinations of these.

The preferred dicarboxylic acid adduct of hexahalocyclopentadiene is1,4,5,6,7,7-hexachlorobicyclo (2.2.1)- 5-heptene-2,3-dicarboxylic acid(commonly called chlorendic acid) because it is readily availablecommercially. Others that can be employed include1,4,5,6,7,7-hexabromobicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid;1,4- 5,6,7,7-hexachloro-2-methylbicyclo-(2.2.1) 5 heptene-2,3-dicarboxylic acid; 1,4,5,6-tetrachloro-7,7 difluorobicycle-(2.2.1) 5heptene-2,3-dicarboxylic acid; l,4,5,6, 7,7-hexachlorobicyclo-(2.2.1) 5heptene 2 acetic 2- carboxylic acid. The halogen inhexahalocyclopentadiene is selected from the group consisting ofchlorine, bromine, fluorine, and mixtures thereof. Typical dicarboxyliccompounds containing aliphatic carbon to carbon unsaturation which canbe used in preparing the dicarboxylic acid adduct include maleic,fumaric, itaconic, citraconic, as Well as longer chain compounds such as3,7-decadienedioic acid, 2-vinyl-5-octenedioic acid, and2,5-divinylhexanedioic acid. The acid halides, acid esters or acidanhydrides can be used in preparing the dicarboxylic acid adduct, withthe acid anhydrides being preferred.

Examples of monomeric 1,2-epoxides include the alkylene oxides having 2to 6 carbon atoms such as ethylene oxide, propylene oxide,butyleneoxide, isobutylene oxide, and 2,3-epoxyhexane. Additionalexamples are 3-ethyl-2,

3-epoxyoctane, epicholorohydrin, epibromohydrin, styrene oxide,glycidol, ,decylene oxide, triphenyl glycidyl silane, allyl glycidylether, methyl glycidyl ether, phenyl glycidyl ether, butyl glycidylsulfide, glycidyl methyl sulfone, glycidylmethacrylate, glycidylacrylate, glycidyl benzoate, glycidyl acetate, glycidyl octanoate,glycidyl sorbate, glycidyl allyl phthalate,phenyl-(p-octadecycloxybenzoyl) ethylene oxide,

OH H CmHaaOCeHiSOzNHCH: /C 3 and the like. The preferred monoepoxidesare the monoepoxide substituted hydrocarbons, the monoepoxy-substitutedethers, sulfides, sulfones and esters wherein the said compounds containno more than eighteen carbon atoms. A lower alkylene oxide is preferablyemployed in rigid foams, as the higher counterparts yield flexiblerather than rigid foams.

In the preparation of the resinous reaction product of the presentinvention, the ratios employed are one mole of hexahalocyclopentadieneadduct to at least four moles of 1,2-epoxide, and preferably not morethan thirty moles of 1,2-epoxide. After the hexahalocyclopentadieneadduct and the 1,2-epoxide are mixed together, the reaction product isheated at a temperature preferably from about fifty to 150 degreescentigrade for preferably from one to 24 hours. The reaction time can beshortened and the temperatures can be lowered by the use of moderatepressure, preferably about 30 to 60 pounds per square inch absoluteinstead of atmospheric, although higher pressures such as up to 500pounds per square inch absolute can be used, if desired. The reaction isalso facilitated by the use of catalysts, although these are notnecessary for the reaction to proceed. Suitable catalysts are compoundssuch as stannous octoate, stannous chloride, and the alkali metalhydroxides, such as the hydroxides of lithium, sodium, rubidium andcesium. Other catalysts that have been used include calcium and bariumcarbonate, dibutyltin dilaurate and triethylene diamine.

It is also contemplated in the present invention to prepare compositionsutilizing a mixture of 1,2-epoxides. A mixture, such as ethylene oxideand propylene oxide, can be reacted with the bicyclic adduct throughoutthe reaction period. Alternatively, one epoxide, such as propyleneoxide, can be reacted during the early stage of the reaction period anda second epoxide such as ethylene oxide, can be introduced to thereaction mixture at a later stage.

Small amounts of by-product that form, probably condensed epoxides, donot adversely affect the characteristics of the product of theinvention.

The resinous reaction products of the present invention are especiallyuseful in the preparation of polyurethane foams. The polyurethane foamscan be prepared by reacting together the resinous reaction product ofthe present invention and an organic polyisocyanate in the presence of afoaming agent and optionally a supplementary hydroxyl-containing polymerand a reaction catalyst, and other additives, if desired.

The polyisocyanate concentration can be varied from about 75 to 125percent of isocyanate groups with respect to the total number ofhydroxyl and carboxyl groups in the resinous reaction product, thehydroxyl-containing polymer, and the foaming agent.

Aromatic isocyanates are preferred because they are more reactive andless toxic than the aliphatic members. Typical isocyanates include thefollowing: 2,4-tlylene diisocyanate; 2,6-tolylene diisocyanate;hexamethylene diisocyanate; ethylene diisocyanate; trimethylenediisocyanate; pentamethylene diisocyanate; 1,2-propylene diisocyanate;1,3-buty1ene diisocyanate; 1,3,5- benzene triisocyanate; polymethylenepolyphenylisocyanate; the liquid reaction products of (l) diisocyanatesand (2) polyols or polyamines, and the like. In addition, mixturesofisocyanates may be employed, aswell as the many impure or crudepolyisocyanates that are commercially available such as crude mixturesof methylene bis(4-phenylisocyanate).

Any foaming agent commonly used in the art can be employed. Suitablefoaming agents are those materials capable ofliberating gaseous productswhen heated, or when reacted with an isocyanate. The preferred foamingagents are the fluorochlorocarbons boiling in the range of twenty tofifty degrees centigrade, and mixtures thereof, for example,trichlorofluoromethane, trichlorotrifluoroethane,dichloromonofluoromethane, monochloroethane, monochloromonofluoroethane,defluoromonochloroethane, difluorodichloroethane. Other foaming agentswhich can be employed include water, a tertiary alcohol and aconcentrated acid such as is disclosed and claimed in US. 2,865,869,polymethylol phenols, dimethylol ureas, polycarboxylic compounds, andformic acid. Mixtures of any of the above foaming agents may also beused. The amount of foaming agent used is not critical, but will bedictated by the type of foam desired. If a very dense foam is desired,only a small amount need be used. If a very light foam is desired, amaximum amount should be used. The amount used will also depend upon theparticular foaming agent.

The catalyst employed can be any of the known conventional catalysts forthe isocyanate reaction, such as tertiary amines, for example,triethylamine, N-methyl morpholine, triethanolamine, and the like, orantimony compounds such as antimony caprylate, antimony naphthenate orantimonous chloride. In addition, tin compounds may be employed such asdibutyltindilaurate, trin-octyltin oxide, hexabutylditin, tributyltinphosphate or stannic chloride.

In the preparation of the polyurethane foams of the present invention itis preferred to blend the resinous reaction product of the presentinvention with a hydroxylcontaining polymer having a hydroxyl number ofbetween about 25 and 900. The resultant product is reacted with anorganic polyisocyanate in the presence of a foaming agent and optionallya reaction catalyst, as above. The total resinous ingredients, that isthe total of the resinous reaction product plus hydroxyl-containingpolymer, should contain at least 20 percent by weight of resinousreact-ion product. It has been found in accordance with the presentinvention that by blending the resinous reaction product of the presentinvention with a hydroxyl-containing polymer, a wide variety ofproperties can be obtained in the resultant polyurethane foam, dependingupon the particular hydroxyl-containing polymer employed and theproportion of hydroxyl-containing polymer to resinous reaction product.

Rigid or flexible polyurethane foams are thereby obtained. The rigidpolyurethane foams utilize a highly branched hydroxyl rich polyester orpolyether having a hydroxyl number of between about 200 and 900. Theflexible polyurethane foams utilize a linear relatively hydroxyl poorpolyester or polyether having a hydroxyl number of between about 25 and100. If a polyester or polyether with a hydroxyl number between aboutand 200 is employed, a semi-rigid polyurethane foam is obtained.

Any hydroxyl-containing polymer having a hydroxyl number of betweenabout 25 and 900 can be used in the present invention, for example apolyester, a polyether or mixtures thereof.

The polyesters are the reaction products of a polyhydric alcohol and apolycarboxylic compound, said polycarboxylic compound being either apolycarboxylic acid, a polycarboxylic acid anhydride, a polycarboxylicacid ester, a polycarboxylic acid halide or mixtures thereof. Among thepolycarboxylic compounds which can be used to form the polyester are:maleic acid; fumaric acid; phthalic acid; tetrachlorophthalic acid; andaliphatic acids such as oxalic, malonic, succinic, glutaric, adipic, andthe like. Additional polycarboxylic compounds which may be used to formthe polyester are Diels-Alder adducts of hexahalocyclopentadiene and apolycarboxylic compound, wherein the halogen is selected from the groupconsisting of chlorine, bromine, fluorine and mixtures thereof, forexample: 1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid; 1,4,5,6-tetra.- chloro 7,7difluorobicyclo (2.2.1)-5-heptene-2,3-dicarboxylic acid;1,4,5,6,7,7-hexabromobicyclo-(2.2.1)-5- heptene-Z,3'dicarboxylic acid;1,4,5,6-tetrabromo-7,7-difluorobicyclo-(2.2.l)-5-heptene-2,3-dicarboxylic acid; and the like.Mixtures of any of the above polycarboxylic compounds can be employed.

To obtain a satisfactory rigid foam, at least a portion of the totalpolyhydric alcohol component should be a polyhydric alcohol containingat least three hydroxyl groups. The condition provides a means forbranching the polyester. Where an even more rigid structure is desired,the whole alcohol component can be made up of a trifunctional alcoholsuch as glycerol. Where a less rigid final product is desired, adifunctional polyhydric alcohol such as ethylene glycol or1,4-butanediol can be utilized as that part of the polyhydric alcoholcomponent. Other glycols such as diethylene glycol, propylene glycol,and the like can also be used. Among the polyhydric alcohols which canbe used as glycerol, hexanetriol, butanetriol, trimethylol propane,trimethylol ethane, pentaerythritol, and the like. The ratio of thepolyhydric alcohol such as glycerol to the polybasic acid can beexpressed as the hydroxyl-carboxyl ratio, which may be defined as thenumber of moles of hydroxyl groups to the number of moles of carboxylgroups in a given weight of resin. This ratio may be varied over a widerange. Generally, however, a hydroxyl-carboxyl ratio of between 1.5 :1to 5:1 is employed.

Instead of employing a polycarboxylic compound which is Diels-Alderadduct of hexahalocyclopentadiene and a polycarboxylic compound, we mayemploy a polyhydric alcohol which is a Diels-Alder adduct ofhexahalocyclopentadiene and a polyhydric alcohol. This can be done byemploying (A) a polyester resin comprised of the re action product of(1) an adduct of hexahalocyclopentadiene and a polyhydric alcoholcontaining aliphatic carbon-to-carbon unsaturation, (2) a polycarboxyliccompound and (3) a polyhydric alcohol containing at least three hydroxylgroups. Typical adducts include 2,3-dimethylol1,4,5,6,7,7-hexachlorobicyclo-(2.2.1)-5-heptene; 2,3 dimethylol1,4,5,6-tetrachloro-7,7-difluorobicyclo- (2.2.l)-5-heptene; and thelike. These compounds and others are disclosed in the copendingapplication Ser. No. 308,922, for Polyhalogen-Containing PolyhydricCompounds filed Sept. 10, 1952, now US. Patent No. 3,007,958. Wherearomatic or bicyclo carboxylic compounds are used, it is often desirableto incorporate aliphatic acids as part of the polyester resin. Suitableacids are adipic, oxalic, succinic, suberic, azelaic, and the like.Unsaturated acids such as maleic, fumaric, itaconic, citraconic, andaconitic can also be used.

The preferred polyesters of the present invention are those whichcontain an adduct of hexahalocyclopentadiene co-reacted in the polyesterportion in view of the fact that they contain a large amount of stablechlorine, thereby enhancing the flame-retardant characteristics of theresultant foam. Particularly preferred are those polyesters wherein theadduct is reacted in the polycarboxylic portion of the polyester, due tolower cost and commercial 6 availability of the polycarboxylic adductsof hexahalocyclopentadiene.

The polyethers employed are the reaction products of (1) either apolyhydric alcohol, a polycarboxylic acid, or a polyphenolic compound,and (2) a monomeric 1,2- cpoxide possessing a single 1,2-epoxy group,such as, for example, propylene oxide. The polyhydric alcohols,polycarboxylic acids, and epoxides which can be employed are any of thepolyhydric alcohols, polycarboxylic acids and monomeric 1,2-epoxideshaving a single 1,2- epoxy group, hereinbefore listed. Suitablepolyphenolic compounds are the phenol-aldehyde resins such asphenolformaldehyde novolac resins.

The fire-resistant surface coatings prepared from the reaction productsof the present invention are prepared by reacting the reaction productsof the present invention with low molocular weight polyesters orpolyethers in the presence of an inert solvent. Alternatively,fire-resistant surface coatings can be obtained by reacting the reactionproducts of the present invention with liquid hydroxyl containingglycerides in the presence of an inert solvent. In each case,appropriate reaction catalysts may be employed if desired.

Fire-resistant elastomers or synthetic rubbers can be obtained byreacting the reaction products of the present invention with a linearpolyester or polyether, preferably in the presence of a reactioncatalyst. The resultant product is then milled, and the like, byprocedures known to the art. Optionally, fillers and modifying agentssuch as are known to the art are employed.

Fire-resistant adhesives can also be obtained in the conventionalmanner. A solvent can be employed, if desired, and the adhesives arepreferably prepared in the presence of a reaction catalyst.

The following examples serve to illustrate the invention, but do notlimit it. All parts are by weight and temperatures in degrees centigradeunless specified otherwise.

Example 1-Preparation of resinous material To a one-liter, three-neckedflask equipped with a mechanical stirrer, therometer, and refluxcondenser and containing 3485 grams (six moles) of propylene oxide isadded 389 grams (one mole) of chlorendic acid with stirring. The acidrapily dissolves in the proyplene oxide with an evolution of heat. Thepotassium hydroxide (004-10 gram) was then aded to the reaction andmixture refluxed for eighteen hours. At the end of this time, the acidnumber of the product was zero. The excess propylene oxide was thendistilled off under vacuum. The residual product was a honey-coloredliquid with a zero acid number, hydroxyl number of 202, and a chlorinecontent of 34.3 percent. This is equivalent of about four moles ofpropylene oxide reacting with each mole of 1,4,5,6,7,7hexanchlorobicyclo (2.2.1)-5-heptene-2,3- dicarboxylic acid,

Example 2.--Preparation of rigid polyurethane foam A resin having ahydroxyl number of 365 was first prepared by adding twelve moles oftrimethylolpropane to a flask containing six moles of chlorendic acidand cooking the mixture at 160 degrees centigrade under a stream ofnitrogen to a zero acid number during which time the water of reactionwas removed by distillation. Then 113 grams of this resin was add-ed toa beaker together with 73.5 grams of the reaction product of Example l,and 0.28 gram of dibutyl tin dilaurate. The mixture was then stirred andheated to 39 degrees centigrade. At this point, a solution of 16.5 gramsof trichlorofluoromethane dissolved in grams of the reaction product of593 grams of chlorendic acid and 1392 grams of tolylene diisocyanat-eisomers, which consisted of a commercial mixture of eighty percent2,4-tollylcne diisocyanate and twenty percent 2,6-diisocyanate, wasadded and the mixture stirred thoroughly for two and one-half minutesduring which time it changed to a creamy mass. The

Example 3.-Prepar'ation of semi-rigid polyurethane foam The followingingredients were blended at room temperature: 150 grams of polyetherwhich had a hydroxyl number of 42 and which was the reaction product ofone mole of trimethylolpropane and 67 moles of propylene oxide; eightgrams of water; two grams of silicone oil; and two grams oftriethylenedia-mine. To this solution was added with rapid stirring 200grams of a semi-prepolymer which was the reaction product of 55 parts oftolylene diisocyanate isomers and 45 parts of the liquid resinousreaction product of one mole of chlorendic acid, and four moles ofpropylene oxide, said liquid resinous reaction product prepared in themanner of Example 1, and having a hydroxyl number of 170. The foam waspermitted to expand at room temperature, then cured for one hour at 120degrees centigrade. The final foam had a density of 22 l'b./ft. had slowrecovery after compression and was self-extinguishing.

Example 4.Preparation of flexible polyurethane foam The followingingredients were blended at room temperature: 330 grams of .polyetherwhich had a hydroxyl number of 42 and which was the reaction product ofone mole of trimethylolpropane and 67 moles of propylene oxide; ninegrams of water; 2.5 grams of silicone oil; and 3.0 grams oftriethylenediamine. To this solution was added with rapid stirring: 220grams of a semi-prepolymer which was the reaction product of 64 partstolylene diisocyanate isomers, and 36 parts of the liquid resinousreaction product of one mole of chlorendic acid, and four moles ofpropylene oxide, said liquid resinous reaction product prepared in themanner of Example 1, and having a hydroxyl number of 170. The foam waspermitted to expand at room temperature, cured for five minutes at 120degrees centigrade, crushed, then cured for one hour at 120 degreescentigrade. The final foam had a density of 2.5 lb./ ft. was resilientand self-extinguishing, and in addition, the melt wasself-extinguishing.

Example 5.Preparation of rigid polyurethane foam The followingingredients were blended at room temperature: 70 grams of the liquidresinous reaction product of one mole of chlorendic acid, and four molesof propylene oxide, said liquid resinous reaction product prepared inthe manner of Example 1, and having a hydroxyl num- 'ber of 170; thirtygrams of trimethylolpropane; 0.5 gram of silicone oil; and 1.0 gram ofN,N,N',-N'-tetramethyl- 1,3-butanediamine. To this solution was addedwith rapid stirring a solution of: 127 grams of semi-prepolymer whichwas the reaction product of 70 parts tolylene diisocyanate isomers and30 parts of the liquid resinous reaction product of one mole ofchlorendic acid and four moles of propylene oxide, said liquid resinousreaction product pre pared in the manner of Example 1, and having ahydroxyl number of 170; and 30 grams of trichlorofluoromethane. The foamwas permitted to expand at room temperature, then was cured at 80degrees centigrade for fifteen minutes. The final foam had a density of2.6 lb./ft. and was self-extinguishing.

Example 6.-Preparation of semi-rigid polyurethane foam parts of tolylenediisocyanate isomers, and 30 parts of the liquid resinous reactionproduct of chlorendic acid, and four moles of propylene oxide, saidliquid resinous reaction product prepared in the manner of Example 1,and having a hydroxyl number of 170. The foam was permitted to expand atroom temperature, then cured at degrees centigrade for one hour. Thefinal foam had a density of 2.8 lb./ft. and was self-extinguishing.

Example 7 The process of the invention was carried out under pressure ina pressure reactor of 1000 ml. capacity, equipped with a stirrer,heating jacket and a Mercoid pressure controller. Initially, 2 moles ofpropylene oxide were reacted with 0.5 mole of chlorendic acid in thepresence of 0.3 weight percent stannous octoate based on the weight ofchlorendic acid. The reaction commenced without heating and wasexothermic, accompanied by a rise in pressure. As the exotherm subsidedand the pressure dropped due to the propylene oxide being consumed, themixture was heated to -110 degrees centigrade. Then, the Mercoidcontroller, sensing pressure, with variable on-olf set points, wasadjusted to maintain a control band of 2040 pounds per square inchgauge. When the pressure dropped below 20 p.s.i.g., as a result ofpropylene oxide consumption, the Mercoid switch closed and the additionpump was activated. Propylene oxide was then pumped into the reactorthrough a line protected by a check valve until the reactor pressure was40 p.s.i.g. At this point the Mercoid switch opened, shutting off thepropylene oxide addition pump. In this manner the addition cycle wasautomatically repeated until an additional 2.7 moles of propylene oxidewere added (and reacted). The addition was then stopped, the reactionmixture transferred to a rotating vacuum evaporator to remove traces ofunreacted propylene oxide. The final product was a resinous materialwith a hydroxyl number of 121. The molecular weight calculated fromhydroxyl number was 928. The chlorine analysis showed 21.6 percentchlorine. The viscosity of this material was 3,700 centiposes at 30degrees centigrade and the Gardner color value was 3. The productcontained 9.3 moles of propylene oxide per mole of chlorendic acid.

Examples 8 to 11 Using the same procedure set forth in Example 7,additional resinous products of the invention were prepared in which theratios of alkylene oxide to chlorendic acid were varied. The propertiesof the resulting compositions are tabulated in Table I.

This invention can be embodied in other forms or carried out in otherways without departing from the spirit or essential characteristicsthereof. The present embodiment is therefore to be considered as in allrespects illustrative and not restrictive, and all changes which comewithin the meaning and range of equivalency are intended to be embracedtherein.

We claim:

1. A fire-resistant polyurethane reaction product of componentscomprising wherein X is a halogen selected from the group consisting offluorine, chlorine, bromine, and mixtures thereof; R is a residue of amonomeric 1,2-epoxide having up to 18 carbon atoms; R and R are selectedfrom the group con sisting of hydrogen and alkyl radicals having 1 to 4carbon atoms; R and R are hydrocarbon radicals having 1 to 6 carbonatoms; y is an integer from to 1; and m and It are integers from 1 towherein m+n is at least 4; and

(H) an organic polyisocyanate.

2. A fire-resistant polyurethane foam product of the reaction ofcomponents comprising wherein X is a halogen selected from the groupconsisting of fluorine, chlorine, bromine, and mixtures thereof; R is aresidue of a monomeric 1,2epoxide having up to 18 carbon atoms; R and Rare selected from the group consisting of hydrogen and alkyl radicalshaving 1 to 4 carbon atoms; R and R are hydrocarbon radicals having 1 to6 carbon atoms; y is an integer from 0 to 1; and m and n are integersfrom 1 to 10; wherein m+n is at least 4;

(II) a hydroxyl-containing polymer having a hydroxyl number betweenabout 25 and 900;

(Ill) an organic polyisocyanate; and

(IV) a foaming agent.

3. The product of claim 2 wherein the hydroxyl-containing polymer is apolyester, polyether or mixtures thereof.

4. A fire-resistant polyurethane foam product of the reaction ofcomponents comprising wherein R is a residue of a monomeric 1,2-epoxidehaving up to 18 carbon atoms, and m and n are integers from 1 to 10,wherein m-t-n is at least 4;

(II) a hydroxyl-containing polymer having a hydroxyl number betweenabout 25 and 900 and selected from the group consisting of a polyester,a polyether and mixtures thereof;

(HI) an organic polyisocyanate; and

(IV) a foaming agent.

5. The product of claim 4 wherein the 1,2-epoxide is an alkylene oxidehaving 2 to 6 carbon atoms.

6. The product of claim 5 wherein the alkylene oxide is propylene oxide.

References Cited UNITED STATES PATENTS 3,055,850 9/1962 WOrsley et al260-25 DONALD E. CZAJA, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

M. B. FEIN, Assistant Examiner.

2. A FIRE-RESISTANT POLYURETHANE FOAM PRODUCT OF THE REACTION OFCOMPONENTS COMPRISING